4-Acetyl-2,3-dimethyl-6-isopropenylmethyl-cyclohexene

ABSTRACT

AND (III) AND A MIXTURE OF COMPOUNDS HAVING THE   II. A mixture of compounds having the structure:   A superatmospheric process for directly producing a Diels-Alder adduct which comprises admixing: I. A conjugated diene which can be either alpha-terpinene, alloocimene, cyclopentadiene or myrcene; with II. A carbonyl group-containing compound which can be either acetone, acetaldehyde propionaldehyde or methylethyl ketone; with III. An aldehyde source which can be either a formaldehyde source or an acetaldehyde source which aldehyde source will yield formaldehyde or acetaldehyde; in the presence of IV. A secondary amine catalyst such as a lower dialkyl amine or a cyclic amine such as morpholine, pyrrolidine or piperidine, AT A TEMPERATURE IN THE RANGE OF FROM ABOUT 120*C up to about 200*C for a period of time from about 2 hours up to about 8 hours, and novel products produced therefrom to wit: I. A mixture of compounds having the structures:

United States Patent [1 1 Hall [ 1 Dec. 30, 1975 14-ACETYL-2,3-DlMETHYL-6- ISOPROPENYLMETHYL-CYCLOHEXENE [75] Inventor:John B. Hall, Rumson, NJ.

[73] Assignee: International Flavors & Fragrances Inc., New York, NY.

22 Filed: Apr. 22, 1974 21 Appl. No.: 462,750

52 U.S.Cl 260/586 R; 252/89; 252/132;

252/368; 252/522; 260/586 C; 260/586 F; 260/586 G; 260/598; 424/69 OTHERPUBLIC ATlONS Buchi et al., J. Am. Chem. Soc., Vol. 92, pp. 3126-3133,(l970) Primary Examiner-Norman Morgenstern Attorney, Agent, orFirm-Arthur L. Liberman, Esq.; Harold Haidt, Esq.

[57] ABSTRACT A superatmospheric process for directly producing aDiels-Alder adduct which comprises admixing:

i. A conjugated diene which can be either alpha-terpinene, allo-ocimene,cyclopentadiene or myrcene; with ii. A carbonyl group-containingcompound which can be either acetone, acetaldehyde propionaldehyde ormethylethyl ketone; with iii. An aldehyde source which can be either aformaldehyde source or an acetaldehyde source which aldehyde source willyield formaldehyde or acetaldehyde; in the presence of iv. A secondaryamine catalyst such as a lower dialkyl amine or a cyclic amine such asmorpholine, pyrrolidine or piperidine,

at a temperature in the range of from about 120C up to about 200C for aperiod of time from about 2 hours up to about 8 hours, and novelproducts produced therefrom to wit:

i. A mixture of compounds having the structures:

and

ii. A mixture of compounds having the structure:

and

and (iii) and a mixture of cornpounds having the structures:

1 Claim, No Drawings 4-ACETYL-2,3-DIMETHYL-G-ISOPROPENYLMETHYL-CYCLOHEXENE BACKGROUND OF THE INVENTION The Diels-Alder reactionis well known in the field of organic chemistry, and the classic examplethereof is the reaction of a conjugated diene with a conjugated alkylenecarbonyl compound to provide a cyclohexene derivative. Since theoriginal reaction was'setforth, there have been many variations of thereaction.

U.S. Pat. No. 3,341,601 issued on Sept. .12, 1967, relates to a processfor producing Diels-Alder adducts of conjugated dienes and carbonylcompounds, wherein the adducts are produced by contacting a reactionmixture comprising a conjugated diene and a carbonyl compound having atleast two alpha-hydrogen atoms with a condensation-dehydration catalystat elevated temperatures according to the following reaction:

cu, cl-r C11 CH H, l HCHO R CH, CHO H CH H --CHO CH1 CH2 Although anin-situ formed methacrolein material is shown to be produced and act asa dienophile in the disclosure of US. Pat. No. 3,341,601, the dienesused in this reaction are 'relativelysimple-in nature.

Although the reaction of long chain aldehydes with formaldehyde in thepresence of an amine catalyst is disclosed in U.S. Pat;' No. 3,463,818,no suggestionof the carrying out of a Diels-Alderreaction is set forththerein. U.S. Pat.'No."3,463,818 relates to a process for producingalpha-methylene-and' alpha-methyl aldehydes and alcohols by reaction, inthe presence of an amine catalyst, an aldehyde such as citronellal withformaldehyde. i

U.S. Pat. No. 2,373,568 shows the Diels-Alder reaction of methacroleinand cyclopentadiene under pressure at about 140C to provide a materialwith a camphoraceous aroma and the further reaction of the Diels-Alderproduct with acetone and sodium methylate to provide a product with afloral-type odor. Vaughan et al in J.A.C.S. 74, 5355 shows the reactionofmesityl oxide and c'yclopent'ailiene produced in'si tu by thermaldepolymerization of the dimer to provide an unsaturated ketone bycarrying' out the reaction at 160C for 12 hours to provide a 21%yield,*based upon mesityl oxide. I 7

Chemical Abstracts 47," 12271e shows a diene condensation at "160C inthe presence of'pyrolgallol.

Chemical Abstracts, Vol. 56, 4692c discloses'the Diels-Alder reaction of'allo-ocimene with appropriate carbonyl compounds such as acrylbnitrileto yield naphthalene derivatives in the"p resence ofhydroquinone at 160-200C for a period of time of from 2 k hoursjupftolf6' hours in 501 71.5%yields Acrolein and allo-ocimene have been shown to react to formDiels-Aldej'r adducts in the presence of hydroquinonc by B. A. Arb,uz0 vand"A R'. Vilchinskaya (State Univ., Kazan). Zhur. Obshc hei Khim. 31,2199204 (1961). 1 f

A. R. Vilchinskayarand B.-A. Arbuzov, Voprosy Khim. Terpenov iTerpenoidov, Akad/Nauk Litovsk, S.S.R., Trudy Vsesoyuz, Soveshchaniya,Vilnyus 1959. 201-7 (Pub. 1960) also showreaction products ofcrotonaldehyde with 'alld-ocim ene (also see v01. 55, CherhicalAbstracts, 16495d).'The Diels-Alder reaction of allo-ocimene withacrolein or crotonaldehyde is also set forth in Vol. 29, ChemicalAbstracts 68886 (Abstract of B erichte 68B, 1435-8 1935). Also suggestedin the Beric hte article 'is the condensation of the thus prodilcedreactiol n products with acetone and other keton esto form 'o'doriferousionone-like compounds. Us. Pat. No. 3,067,244 discloses, interalia,'thecatalyzed condensation of cyclopentadiene with acrolein.

' British Pat.' No." 89 6,03'9 entitled Method of Producin'gD'erivatives'of the 1,1-Dimethyl-octahydronaph thalene Series disclosesthe generic process:

wherein R R and R are disclosed to be same or different hydrogen atomsor alkyl and R is disclosed to be hydroxy, alkyl or alkoxy. The Britishpatent discloses this process to be useful for producing productsresembling the well known class of violet perfumes". Indeed, Example 5of the British patent alleges that the compound 1,1,6,6-tetramethyl-7-ketomethyl-octalin produced by (l) reacting myrceneand mesityl oxide thermally followed by (2) subsequent cyclization, hasa pleasant woody ambergris smell.

Further, cyclization reactions of Diels-Alderadducts of myrcene and adienophile are set forth in U.S. Pat. No. 3,076,022. This patentdiscloses interalia, preparation of the thermal Diels-Alder adduct ofmyrcene and methyl isopropenyl ketone and subsequent acid cyclization toa product said to possess an intense ambergris-like note v. I

.Ohloff (Chemistry of Odoriferous and Flavoring Substances) pp. -240 (atpage 192) Fortschritte J der Chemischen Forschung Vol. 12, Part 2, 1969,discloses a compound having the structure:

Ohloff indicates that materials of this nature have resiny odorslikeolibanum, with amber type undertones.

THE INVENTION This invention relates to the preparation of syntheticwoody or floral, melony, or green, woody, herbaceous or'citrusyfragrance ingredients for perfumes and cos-- ii. mixture of compoundshaving the structures:

anal

iii. and a mixture of compounds having the struc tures:

The invention also covers processes for producing, directly, Diels-Alderadducts which process comprises intimately admixing:

i. A conjugated diene selected from the group consisting ofalpha-terpinene, allo-ocimene, cyclopentadlene and myrcene; with ii. acarbonyl group-containing compound selected from the group consisting ofacetone, acetaldehyde, propionaldehyde and methyl-ethyl ketones; withiii. an aldehyde source selected from the group. consisting of aformaldehyde source and an acetaldehyde source; and

iv. a secondary amine catalyst.

A particular feature of my invention is that the dienophile (thecondensation products which are obtained by the reaction of thecarbonyl-group-containing compound and the aldehyde source) immediatelyreacts with the conjugated diene, thus forming the Diels- Alder adduct.The dienophiles may be considered as being acrolein, methacrolein,methyl vinyl ketone and 3-methyl pent-3-en-2-one. The decisiveadvantages of the instant process are:

i. many low molecular weight substituted acroleins and alpha,beta-unsaturated ketones are skin, eye and respiratory irritants andtherefore, at best, unpleasant to handle;

ii. the great reactivity of acrolein, alpha-substituted acroleins andlow molecular weight alpha-betaunsaturated ketones makes them unsuitablefor storage without decomposition; and

iii. more efficient processing is accomplished by combining theformation of the dienophile with the Diels- Alder reaction withouthaving two separate reactions to carry out in a manufacturing operation.

The resulting adducts are useful per se as perfumery materials, havinggreen-floral odors or they may be furtherreacted asbyv cyclization asfurther exemplified herein to form other materials which are useful inperfumery for their amber-like or fruity or fruity-amber or woody, orgreen or yeasty or buttery or ionone-like or pineapple-like fragrancesand which are useful in tobacco because they modify the aromas of themainstream and side-streams of a smoking article on smoking by impartingto the aroma of such mainstream and sidestream sweet, spicey,cedarwood-like notes.

The basic process of our invention involves heating a mixture of aconjugated diene with the carbonyl groupcontaining compound, and thealdehyde source, and a secondary amine catalyst in an autoclave atpressures substantially greater than atmospheric at temperatures in therange of 120C up to 200C for a period of time of from 2 hours up to 8hours.

The conjugated diene in our invention is specific and may be one of thefollowing materials:

i. alpha-terpinene;

ii. allo-ocimene;

iii. cyclopentadiene; or

iv. myrcene Myrcene is commercially available in purities of 70% andupwards, and it can be used in this form. ltis generally preferred inthe practice of this invention to use commercial myrcene (approximately72-77% purity), although, obviously, purified myrcene may be used. Sucha purification is readilyaccomplished by fractional distillation. 1 I

The carbonyl group-containing compound is also specific in the processof our invention and may be either:

i. acetone;

ii. acetaldehyde;

iii. propionaldehyde; or

iv. methyl-ethyl ketone 1 It is preferred that the purity of thealdehyde or ketone be between 90 and 100%; preferably as close to 100%as possible,'in order to avoid purification problems at the end of thereaction.

The aldehyde source which is selected from the group consisting of aformaldehyde source and an acetaldehyde source may be one of thefollowing materials:

i. paraformaldehyde (a formaldehyde polymer of high molecular weightwhich depolymerizes at the reaction temperature);

ii. formalin (a 40% solution of formaldehyde containing a small amountof methanol); or

iii. acetaldehyde The catalyst used is a secondary amine, preferablydiethyl amine or dimethyl amine which may be in the form of a salt ofthe amine with an inorganic acid such as dimethyl amine sulfate anddiethyl amine sulfat. Other secondary amines which are suitable for theinstant reaction are as follows:

Methyl ethyl amine Methyl n-propyl amine Methyl isopropyl amine Ethylisopropylamine Ethyl n-butyl amine Ethyl t-butyl amine PyrrolidinePiperidine Morpholine The amine catalyst may be introduced into thereaction mass as such, in the gaseous phase, or in solution, forexample, in aqueous solution. The catalyst, when used as a salt, may bepreformed or it may be formed in-situ in the reaction mass. Thus, forexample, the secondary amine may be first introduced into the reactionmass, followed by the mineral acid which will form the amine salt.

Theoretically, the mole ratio of conjugated diene: carbonylgroup-containing compoundzaldehyde source is 1:;l.:l. Nevertheless, itis preferred to use a slight excess of aldehyde {source with respect tocarbonyl group-containing compound and conjugated diene. Also, it ispreferred to use a slight molar excess of carbonyl group-containingcompound with respect to conjugated diene. The mole ratio of secondaryamine: conjugated diene is preferably between 1:20 and 1:5. Excess aminecatalyst gives rise to problems concerning work-upiafterthe completionof the reaction. Too little amine catalyst will cause the reaction to beinordinately slow, and therefore commercially impractical.

The reaction temperature can vary from 120C up to 200C, with atemperature range of l50C-l C being preferred. At lower temperatureslonger reaction times are required. In view of the nature of thecatalyst used,

the temperature of l20,200 C gives rise to the use .of pressures higherthan atmospheric. Accordingly, the use of pressure reaction vessels arerequired.

The order of addition of reactants and catalyst is not critical;however, it is preferred to pre-mix the conjugated diene, aldehydesource and carbonyl group-containing compound prior to addition of thesecondary amine catalyst. Furthermore, it is preferred to pre-mix thesecondary amine with the conjugated diene, carbonyl group-containingcompound and aldehyde source prior -to addition of the mineral acid(when desired) whereby the catalyst salt will be produced.

In carrying out the reaction, it is preferable to use an acid pH ofbetween about 3 and about 6. Nevertheless, a pH of upto 8 will not bedetrimental to the reaction.

The following table sets forth the type of reaction product. which willbe produced using the aforementioned reactants:

TABLE I structuressj of Productgsz Reactants Conjugated Diene CarbonylGroup-Containing Compound Aldehyde Source formalin L l i}, -continuedTil ntinued Reactants SfructureLs) o! Produet(s) Reactants Structure 8 fProduct Conjugated Diene 5 Conjugated Diene Carbonyl Group-ContainingCarbonyl Group-C ontaining Compound Compound A1 rlvhvde Source AldehydeSource Myrcene 0 Myrc one 0 Ace taldehyde l 0 He thylc thyl ke tone I IFormalin H Formalin u C O Cyclopentadi one Myrc ene O PropionaldehydeAce tone l Formalin \H Formalin Allo-oc imene Ace tone Formalin 3 5 O 40Myrcenq 0 Me thyl-e thyl ke tone Acetaldehyde c H Alpha- Te rpinene Ac etone Formalin so I O i C and new I Conjugated Diene CarbonylGroup-Containing Compound Aldehyde Source Structures) of Products 8)'A'llo-ociinene Propionaldehyde Paraformaldehydo p and.

When the "reaction is substantially complete, the reaction mass is thenwashed and the organic layer is separated and distilled.

The distilled product may be used as is in perfumery or it may be, incertain cases, further reacted, as by cyclization of the compound:

using concentrated phosphoric acid to form a compound having thestructure:

or woody or green or yeasty or buttery or ionone-like or pineapple-likeodors.

The products produced by the process of my invention, including my novelmixtures, and an auxiliary perfume ingredient including, for example,alcohols, aldehydes, nitriles, esters, cyclic esters and naturalessential oils may be admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain (a) the main note or the bouquet orfoundation stone of the composition; (b) modifiers which round off andaccompany the main note; (c) fixatives which include odorous substanceswhich lend a particular note to the perfume throughout all states ofevaporation and substances which retard evaporation; and (d) topnoteswhich are usually low boiling fresh smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics but the over-all effect of theperfume composition will be the sum of the effects of each of theingredients. Thus, the products produced by the process of my inventionincluding my novel mixtures can be used to alter the aromacharacteristics of a perfume composition, for example, by utilizing ormoderating the olfactory reaction contributed by another ingredient inthe composition. v

The amount of the products produced by the process of my inventionincluding my novel mixtures which will be effective in perfumecompositions depend on many factors including the other ingredients,their amounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.05% of the productsproduced by the process of my invention,including my novel mixtures, oreven less can be usedto impart an amber-like, fruity, or fruity amber orwoody or green or yeasty or buttery or ionone-like or pineapple-liketype scent odor to soaps, cosmetics and other products. The amountemployed can range up to 5% of the fragrance components and will dependon considerations of cost, nature of the end product, the effect desiredon the finished product and the particular fragrance sought.

The products produced by the process of my invention including my novelmixtures are useful in perfume compositions as olfactory components indetergents and soaps; space odorants and deodorants; perfumes; colognes;toilet water; bath preparations such as bath oils and bath solids; hairpreparations such as lacquers, brilliantines, pomades and shampoo;cosmetic preparations such as creams, deodorants, hand lotions andsunscreens; powders such as tales, dusting powders, face powders and thelike. When used as an olfactory component of a perfumed article, aslittle as parts per million of the products produced by the process ofmy invention, including my novel mixtures, will suffice to impart lowkeyed amber-like, fruity, or fruity-amber or woody or green or yeasty orbuttery or ionone-like or pineapple-like characteristics. Generally, nomore than 0.5% of the products produced by the process of my invention,including my novel mixtures based on the ultimate end product isrequired in the perfume composition.

In addition, the perfume composition or fragrance compositions of thisinvention contain a vehicle or carrier for the products produced by theprocess of my invention, including my novel mixtures. The vehicle can bea liquid such as an alcohol, a non-toxic alcohol, a non-toxic glycol orthe like. The carrier can also be an absorbent solid such asa gum (e.g.,gum arabic) or components for encapsulating the composition (such asgelatine).

It will thus be apparent that the products produced by the process of myinvention, including my novel mixtures, can be utilized to alter thesensory properties, particularly organoleptic properties such as flavorand- /or fragrances of a wide variety of consumable materials.

In making the perfumes using the materials produced by the instantinvention, such materials can be combined with auxiliary perfumeadjuvants, including one or more of many types of odor materials such asbergamot oil, vetiver oil, patchouli oil, sandalwood oil, oakmoss andfloral musk. The materials produced according to this invention can alsobe combined with a customary perfume auxiliary adjuvants such as naturaloils, synthetic oils, aldehydes, ketones, carboxylic acid esters, arylalcohols, alkanols, lactones, saturated hydrocarbons, unsaturatedhydrocarbons, fixatives, solvents, dispersants, surface active agents,aerosol propellants and the like.

The following examples serve to illustrate embodiments of our inventionas it is now preferred to practice it. It will be understood that theseexamples are illustrative, and the invention is to be consideredrestrictive thereto only as indicated in the appended claims.

EXAMPLE I Into a liter reaction flask equipped with stirrer, refluxcondenser, thermometer and addition funnel, the following materials areadded:

Myrcene 1308 g (6.98 moles) Formalin (37% formaldehyde) 652 g (8.04moles) Propionaldehyde (97.5%) 464 g (7.80 moles) Diethyl amine (58g/0.795 moles) is added to the reaction mass with external cooling, asneeded, to keep the temperature below 25C.

50% wt/wt sulfuric acid (80 g/0.392 moles) is added to the reaction masswith external cooling, as needed, to maintain the temperature below 25C.The pH of the reaction mass at this point is between 5 and 6.

The above-formed reaction mass is charged to a one gallon high pressureautoclave. The autoclave is sealed and operated at 150C and 130 psigpressure for 3 hours.

The reaction mass from the autoclave is then added to a 5 liter reactionflask, and 500 g of aqueous sodium carbonate is added with stirring. Themixture is then refluxed for 3 hours, after which it is cooled to -25C.The aqueous layer is removed and 750 ml toluene is added to the organiclayer. The organic layer is washed successively with one 200 ml portionof 5% sulfuric acid, one 200 ml portion of water, one 200 ml EXAMPLE-" Aprocedure is carried out in accordance with Example l, except'that theautoclave is operated over a period of 5 hours rather than the 3 hourperiod indicated in Example 1. The resulting yield is 69.8% of theory.

EXAMPLE Ill The procedure is carried out in accordance with the processof Example I, scaled up so that moles of myrcene is used and dimethylamine gas is used instead of diethyl amine. The autoclave is operatedfor a period of 5 hours at C. The resulting chemical yield is 80.0%.

EXAMPLE lV A process is carried out in accordance with the process ofExample 1 except that the autoclave reaction is carried out for a periodof 5 hours at C. The resulting chemical yield"is 67.4%.

EXAMPLE v A process according to Example 1 iscarried out except thatinstead of using diethyl amine, dimethyl amine is used as a catalyst,and the reaction is carried out in the autoclave for a period of 5 hoursat 180C. The resultant chemical yield is 69%.

EXAMPLE VI Into a 5 liter reaction flask equipped with stirrer, refluxcondenser,'thermometer and addition funnel, the following materials areadded:

Myrcene (72.6%) 1,308 g (6.98 moles) Acetone 464 g (8.00 moles) Formalin(37%) i 652 g (8.04 moles) The contents of the reaction vessel arecooled to 10C, and 58 g (0.795 moles) of diethyl amine are added withexternal cooling, as needed, to keep the temperature of the reactionmass below 25C. 80 g of 50% wt/wt sulfuric acid (0.392 moles of sulfuricacid) is added to the reaction mass with external cooling, as needed, tomaintain the temperature below 25C. The reaction mass is then charged toa one gallon autoclave, and the autoclave is sealed. The contents of theautoclave are The structure of the resulting product is the same asheated, with stirring at 150C and 150 psig pressure for that obtained inExample Vl.

a period of hours. Toluene (lOO ml) is added to the i EXAMPLE VI"reaction mass from the autoclave,and the material is washed successivelyas follows: Toa solution of 1,308 g of myrcene (72.6%) 352 g of i. one 1liter portion of water; acetaldehyde and 546 g of m ethyl-ethyhketone isii. one 500 ml portion of sulfuric acid; added 240 g of an aqueoussolution containing 72 g of iii. one 500 ml portion of water; diethylamine and 99 g of concentrated sulfuric acid iv..one 500 ml portion ofwater; 10 and l .g of addltlonaldiethyl amine. The rleact on mlaess v.one 500 ml portion of 5% sodium bicarbonate; is-charged to an autoclave,and the auto c ave 1S sea vi. one 1 liter portion of water and stirredfor a period of 5 hours at C and 75l The solvent is stripped off and theresidue is distilled psig pressure. At the end'of this period of timethe rapidly at a vapor temperature of 128 |29C d a autoclave contentsare emptied and 100 cc of toluene pressure of 2.0-2.1 mm Hg to give aproduct h vi h 15 are added to the reaction mass. The reaction mass isstructure: then, successively washed as follows:

EXAMPLE V i. one 1 liter portion of water;

ii. one 1 liter portion of water; iii. one 500 cc portion of 5% sodiumbicarbonate solution; iv. one 500 cc portion of water 100 cc of tolueneare added and the material is distilled Diethyl mine 37 s rapidly at avapor temperature of l24l6lC and a Toluene 250 g pressure of 1.5-2 mmHg. Distillation at a vapor temperature of ll0-l50C and a pressure of2.0-2.5 mm

While maintaining the temperature at 30C, 52 g of Hg gives a productconsisting of a mixture of the strucwt/wt sulfuric acid is added. 1,410g of 77% myrtures:

Into a 3 liter reaction flask equipped with stirrer, thermometer andreflux condenser, the following mate- 30 rials are added:

cene and 580 g of acetone are then added to the reacas confirmed by GLC,NMR, IR and mass spectral tion mass. The resulting reaction mixture isthen transanalysis. ferred to a one gallon autoclave and 158 g ofparaformaldehyde is added thereto. The autoclave is 60 EXAMPLE IX sealedand the contents stirred at C for a period of 5 hours. The resultingreaction product is then added to a 5 liter reaction vessel, to which 1liter of toluene is added. The aqueous layer is drained off and theorganic layer is washed successively as follows:

Into a 5 liter reaction flask equipped with stirrer, reflux condenser,thermometer and addition funnel, the following materials are added:

v 6 Myrcene 77% 1,235 7.0 moles) i: one 500 ml portion of 5% sulfuricacid; Formalin (37% formaldehyde) 495 g (6.1 moles) 11. one 500 mlportion of water; a Methyl Ethyl Ketbne 432 g (61) moles) iii. one 500ml portion of 5% sodium bicarbonate; 500 ml of toluene is added to thereaction mass which is then stripped and rapidly distilled at a vaportemperature of l74l82C and a pressure of 2.9-3.0 mm Hg.

Diethyl amine (43 g/0.603 moles) is added to the reaction mass withexternal cooling, as needed, to keep the temperature below 25C.

50% wt/wt sulfuric acid (62 g/0.605 moles) is added to the reaction masswith external cooling, as needed, to maintain the temperature below 25C.The pH of the reaction mass at this point is between and 6. Theabove-formed reaction mass is charged to a one gallon high pressureautoclave. The autoclave is sealed and operated at 160C for a period of6 hours.

The reaction mass now exists in two phases. The aqueous phase isseparated from the organic phase, and the aqueous phase is extractedwith one 200 cc portion of toluene. The toluene extract and the organicphase are combined and washed as follows:

i. one 500 cc portion of 50% phosphoric acid;

ii. one 500 cc portion of water;

iii. one 500 cc portion of 10% sodium carbonate;

iv. one 500 cc portion of water;

v. one 500 cc portion of saturated sodium chloride The reaction mass isthen stripped of toluene solvent and distilled rapidly at a vaportemperature of 143-178C and a pressure of 3.0-4.5 mm Hg. The crudeproduct is then fractionated on a Goodloe column at a vapor temperatureof 120127C and a pressure of 2.2-2.5 mm Hg, yielding a product which isa mixture of chemical compounds having the structures:

O C H as confirmed by NMR, IR and mass spectral analysis.

EXAMPLE XI Into a 5 liter reaction flask equipped with stirrer, refluxcondenser, thermometer and addition funnel, the following materials areadded:

Allo-ocimene (91.3%) Formalin (37%) Acetone 1,200 g (8 moles) 568 g (7moles) 464 g (8 moles) y CW 7 of EXAMPLE X Into a reaction flask, withstirring and cooling, the following materials are added:

Formalin (37%) Diethyl amine Sulfuric acid (50%) 850 g (10.5 moles) 73 g(1.0 moles) 102 g (0.5 moles) 550 g (9.5 moles) of propionaldehyde, 660g of dicyclopentadiene and 100 g of toluene are then added to thereaction mass. The contents of the reaction mass are then added to anautoclave, and the autoclave is sealed. The autoclave is operated for aperiod of 7.5 hours at 165C and 50-55 psig pressure. At the end of thisperiod of time, the autoclave contents are emptied into a flask andcombined with 1 liter of toluene. The aqueous phase is separated andextracted with one 200 cc portion of toluene, and the toluene andorganic layers are combined and washed as follows:

i. one 250 cc portion of 5% sulfuric acid;

ii. two 250 cc portions of water;

iii. one 250 cc portion of 5% sodium bicarbonate solution iv. one 250 ccportion of saturated sodium chloride solution.

The crude materialfrom several runs made in this way was distilled at46-53C and 2.6-3.1 mm Hg. to give a product having the structure:

autoclave is operated for a period of 5 hours at a temperature of C and50-150 psig pressure. After this period of time, the autoclave isopened, and the aqueous phase is extracted with 250 cc of toluene andthe organic phase and toluene extract are combined and washed asfollows:

i. one 250 cc portion of 5% sulfuric acid;

ii. two 500 cc portions of 10% sodium chloride;

iii. one 250 cc saturated sodium chloride solution The reaction mass isstripped of toluene and rapidly distilled at 98-128C and a pressure of3.7-4.2 mm Hg. The resulting product is a mixture of compounds havingthe structure:

as confirmed by GLC, NMR and IR analysis.

EXAMPLE XII Alpha-terpinene 800 g Formalin (37%) 584 g Acetone 557 gDiethyl amine 53 g 50% Sulfuric acid 75 g The autoclave is sealed andthe reaction mass is heated to 150C and maintained at that temperaturefor a period of 5 hours. At the end of that period of time the autoclaveis opened and the reaction mass is removed. The aqueous phase isseparated from the organic phase, and theorganic phase is washed withone 200-ml portion of 5% phosphoric acid, and then one 200 ml portion ofwater. The reaction product is rushedover and fractionally distilled toyielcla product having an intense woody aroma, having astructureconfirmed by NMR, IR and mass spectral analysis to be:

and

EXAMPLE XIII Into a liter reaction flask equipped with stirrer, refluxcondenser,- thermometer and addition funnel the following materials areadded:

1,200 g (8.0 moles) 568 g (7 moles) 406 g (7 moles) Allo-ocimene (91.3%)Formalin 37%) Propionaldehyde The mixture is'co ole'di as needed, tohold the temperature below C and 58 g (0.795 moles) of diethyl amine and81 g of wt/wt sulfuric acid are added successivelyfThe reaction mass isthen charged to a one gallon autoclave and then stirred at 120C for 2hours and at 150C for 3 hours. At the end of this period of time thereactionmass is removed from the autoclave and the aqueous phase isextracted with one 250cc portion of toluene. The organic phase and thetoluene extract are combined and washed as follows:

i. one 500 ml portion of 10% sulfuric acid;:

ii. one' 500 ml portion of water;

iii. one 500 ml portion of 10% sodium chloride;

iv. one 500 ml portion of saturated sodium chloride 5 g of calciumcarbonate is added to the resulting product, and the reaction mass isstripped of toluene and rapidly distilled at 92-l 14C and 3 mm Hgpressure. The crude product was fractionated using a 12-inch Goodloecolumn at 107-1 l 1C vapor temperature and 2.0-2.3 mm Hg pressure. Theresultant product, as confirmed by NMR, IR and mass spectral analysis isa mixture of materials having the following structures:

EXAMPLE XlV Phosphoric acid 500 g Toluene The material produced by theprocess of Example 1 having the structure:

6E H ml is added to the reaction mass, dropwise, over a period of 1.5hours with cooling as needed in order to maintain the temperature of thereaction mass at 5055C. The reaction mass is maintained at 5055C withstirring for a period of three hours. The reaction mass is then cooledto 2025C and 500 ml of wateris added. The reaction mass now exists intwo phases: an organic phase and an aqueous phase. The two phases areseparated and the aqueous phase is extracted with 250 ml of toluene. Thetoluene extracted and the organic phase are combined and washedsuccessively as follows:

i. two 250 ml portion of 10% aqueous sodium carbonate;

ii. one 250 ml portion of saturated sodium chloride. The solvent isstripped off and the reaction mass is rushed over at 200C and 3 mm Hgpressure. The crude product is then distilled on an 18-inch Goodloepacked column to give the desired product having the structure:

Addition to this floral muguet formulation of 105 parts of the productproduced according to Example I imparts to it a floral melony note.

EXAMPLE XVl The following formulation is prepared:

FLORAL MUGUET Addition to the above formulation of I05 parts of theproduct produced according to Example XlV imparts to this formulation afloral melony note.

EXAMPLE XVll The following formulation is prepared:

i FLORAL MUGUET (1 Ingredients Parts by Weight H Benzyl Acetate l50Geraniol I00 Citronellol 80 p-t-butylphenyl propionaldehyde I00 Hydroxycitronellal I00 Coumarin l0 Vanillin l0 n-undecanal 5 Phenyl EthylAlcohol I00 Beta-lonone 50 Alpha Methyl lonone 50 EXAMPLE Xv CinnamicAlcohol lg) l d l l0%' (1' thl hthalt The following formulation lSprepared: 'lnf l cinnli mi c Alheli dw e) 50 Linalool 40 Linalyl Acetate20 FLORAL MUGUET Vetivert Bourbon 4 lngred'em Pans by we'ght BergamotRectified 20 Benzyl Acetate 150 G l $1323 38 Additlon to the aboveformulation of I05 parts of the p-t-butylphenyl propionaldehyde I00product produced according to Example Xll imparts to Hydroxy cmoneua'this floral mu uet formulation a subtle wood note (\llourflarin 10 g yam in 5 n-undecanal 1 EXAMPLE XVIII Phen l Eth l Alcohol Beta-lonon 50The following formulation .is prepared: Alpha-Methyl lonone 50 CinnamicAlcohol 10 lndole (10% in diethyl phthalate) 5 65 FLORAL MUGUET p-HexylCinnamic Aldehyde 50 Ingredients Parts by Weight Linalool 40 LinalylAcetate 20 Benzyl Acetate Vetivert Bourbon 4 GFRmIOI 7 I00 BergamotRectified 20 c'mmellol 8O p-t-butylphenyl propionaldehyde I00 -continuedFLORAL MUGUET Ingredients Parts by Weight I-Iydroxy Citronellal ICoumarin 10 Vanillin n-undecanal 100 Beta-Ionone 50 Alpha Methyl lonone50 Cinnamic Alcohol l0 lndole in diethyl phthalate) 5 p-Hexyl CinnamicAldehyde 50 Linalool 40 Linalyl Acetate Vetivert Bourbon 4 BergamotRectified 20 Benzyl Benzoate 40 Addition to this floral muguetformulation of 65 parts of the product produced according to Example XVimparts to the formulation a green, woody, herbaceous note.

EXAMPLE XIX The following formulation is prepared:

FLORAL MUGUET Ingredients Parts by Weight Addition to this floral muguetformulation of 65 parts of the product produced according to ExampleXIII imparts to the formulation a green, woody, herbaceous note.

EXAMPLE XX Preparation of Soap Composition One hundred grams of soapchips are mixed with one gram of the perfume composition of Example XVuntil a substantially homogeneous composition is obtained. The perfumedsoap composition exhibits a floral muguet characteristic with a floralmelony note.

EXAMPLE XXI Preparation of a Detergent Composition A total of 100 gramsof a detergent powder is mixed with 0.15 grams of the perfumecomposition of Example XV until a substantially homogeneous compositionis prepared. This composition exhibits a floral muguet fragrance, with afloral, melony note.

EXAMPLE XXII Preparation of a Cosmetic Powder Composition A cosmeticpowder is prepared by mixing in a ball mill I00 grams of talcum powderwith 0.25 grams of the product produced by the process of Example I. Ithas an excellent floral melony aroma.

EXAMPLE XXIII Perfumed Liquid Detergent Concentrated liquid detergentwith a rich floral melony character are obtained containing 0.10%, 0.15%and 0.20% of the product produced by the process'o f Example I. They areprepared by adding and homogeneously mixing the appropriate quantity ofthe produce the process of Example I in the liquid detergent. Thedetergents all possess a floral melony fragrance, the intensityincreasing with greater concentrations of the product produced by theprocess of Example I.

EXAMPLE XXIV Cologne The product produced by the process of Example I isincorporated in acologne at a concentration of 2.5% in aqueous ethanol;and into a handkerchief perfume at a concentration of 5% (in aqueousethanol). A distinct and definite floral melony fragrance is imparted tothe cologne and to the handkerchief perfume.

EXAMPLE XXV The composition of Example XVI is incorporated in a cologneat a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol).The composition of Example XVI affords a distinct and definite strongfloral muguet fragrance with a floral melony note to that handkerchiefperfume and cologne.

EXAMPLE XXVI Preparation of Soap Composition One hundred grams of soapchipe are mixed with one gram of the perfume composition of Example XVIIuntil a substantially homogeneous composition is obtained. The perfumedsoap composition exhibits a floral muguet characteristic with a woodynote.

EXAMPLE XXVII Preparation of a Detergent Composition A total of grams ofa detergent powder is mixed with 0.15 grams of the perfume compositionof Example XVII until a substantially homogeneous composition isprepared. This composition exhibits a floral muguet fragrance with awoody note.

EXAMPLE XXVIII Preparation of a Cosmetic Powder Composition A cosmeticpowder is prepared by mixing in a ball mill 100 grams of talcum powderwith 0.25 grams of the product produced by the process of EXample XII.It has an excellent woody aroma.

EXAMPLE XXIX Perfumed Liquid Detergent Concentrated liquid detergentwith a rich woody character are obtained containing 0.10%, 0.15% and0.20% of the product produced by the process of Example XII. They areprepared by adding and homogeneously mixing the appropriate quantity ofthe product produced by the process of EXample XII in the liquid 23detergent. The detergents all possess a woody fragrance, the intensityincreasing with greater concentrations of the product produced by theprocess of Example XII.

EXAMPLE XXX Cologne The product produced by the process of Example XIIis incorporated in a cologne at a concentration of 2.5% in 85% aqueousethanol; and into a handkerchief perfume at a concentration of (9n 95%aqueous ethanol). A distinct and definite woody fragrance is imparted tothe cologne and to the handkerchief perfume.

EXAMPLE XXXI The composition of Example XVII is incorporated in acologne at a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of (in 95% aqueous ethanol). Thecomposition of Example XVII affords a distinct and definite strongfloral muguet fragrance (with a distinctive woody note) to thathandkerchief perfume and cologne.

EXAMPLE XXXII Preparation of Soap Composition One hundred grams of soapchips are mixed with one gram of the perfume composition of ExampleXVIII until a substantially homogeneous composition is obtained. Theperfumed soap composition exhibits a floral muguet characteristic with awoody, green, herbaceous note.

EXAMPLE XXXIII Preparation of a Detergent Composition A total of 100grams of a detergent powder is mixed with 0.15 grams of the perfumecomposition of Example XVIII until a substantially homogeneouscomposition is prepared. This composition exhibits a floral muguetfragrance with a woody, green, herbaceous note.

EXAMPLE XXXIV Preparation of a Cosmetic Powder Composition A cosmeticpowder is prepared by mixing in a ball mill 100 grams of talcum powderwith 0.25 grams of the product produced by the process of Example XI. Ithas an excellent woody, green, herbaceous aroma.

EXAMPLE XXXV Perfumed Liquid Detergent EXAMPLE XXXVI Cologne The productproduced by the process of Example X1 is incorporated in a cologne at aconcentration of 2.5% in aqueous ethanol; and into a handkerchiefperfume at a concentration of 5% (in aqueous ethanol). A distinct anddefinite woody, green, herbaceous fragrance is imparted to the cologneand to the hand kerchief perfume.

EXAMPLE XXXVII The composition of Example XVIII is incorporated in acologne at a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol).The composition of Example XVIII affords a distinct and definite strongfloral muguet fragrance (with a distinctive woody, green, herbaceousnote) to that handkerchief perfume and cologne.

EXAMPLE XXXVIII Preparation of Soap Composition One hundred grams ofsoap chips are mixed with one gram of the perfume composition of ExampleXIX until a substantially homogeneous composition is obtained. Theperfumed soap composition exhibits a floral muguet characteristic with awoody, green, herbaceous note.

EXAMPLE XXXIX Preparation of a Detergent Composition A total of grams ofa detergent powder is mixed with 0.15 grams of the perfume compositionof Example XIX until a substantially homogeneous composition isprepared. This composition exhibits a floral muguet fragrance with awoody, green, herbaceous note.

EXAMPLE XL Preparation of a Cosmetic Powder Composition A cosmeticpowder is prepared by mixing in a ball mill 100 grams of talcum powderwith 0.25 grams of the product produced by the process of Example XIII.It has an excellent woody, green, herbaceous aroma.

EXAMPLE XLI Perfumed Liquid Detergent Concentrated liquid detergent witha rich woody, green, herbaceous character are obtained containing 0.10%,0.15% and 0.20% of the product produced according to the process ofExample XIII. They are prepared by adding and homogeneously mixing theappropriate quantity of the product of Example XIII in the liquiddetergent. The detergents all possess a woody, green, herbaceousfragrance, the intensity increasing with greater concentrations of theproduct of the process of Example XIII.

EXAMPLE XLII Cologne The product produced by the process of Example XIIIis incorporated in a cologne at a concentration of 2.5% in 85% aqueousethanol; and into a handkerchief perfume at a concentration of 5% (in95% aqueous ethanol). A distinct and definite woody, green, herba ceousfragrance is imparted to the cologne and to the handkerchief perfume.

EXAMPLE XLlIl The composition of Example XIX is incorporated in acologne at a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol).The composition of Example XIX affords a distinct and definite strongfloral muguet fragrance (with a distinctive woody, green, herbaceousnote).

What is claimed is:

1. A mixture of chemical compounds having the structures:

1. A MIXTURE OF CHEMICAL COMPOUNDS HAVING THE STRUCTURES: